EP0168608A2 - Substituted carboxylic-acid anilides - Google Patents

Abstract

New substituted carboxylic acid anilides of the formula <IMAGE> in which X represents oxygen or sulfur, R¹ represents hydrogen, halogen, alkyl having 1 to 6 carbon atoms, trifluoromethyl, optionally substituted phenyl, alkoxy having 1 to 6 carbon atoms or alkyl mercapto having 1 to 6 carbon atoms , R² is halogen or methyl, n is 0, 1 or 2, R³ is hydrogen, halogen, optionally substituted alkyl having 1 to 6 carbon atoms, optionally substituted aryl, optionally substituted aralkyl or for the radicals -OR <6> or - SOm -R <6>, where R <6> stands for optionally substituted alkyl having 1 to 6 carbon atoms or for optionally substituted aryl and m stands for 0, 1 or 2, and R <4> and R <5> independently of one another stand for halogen or optionally substituted alkyl having 1 to 6 carbon atoms or R 4 and R 5 together with the adjacent carbon atom for an optionally substituted seeded saturated or unsaturated carbocyclic ring with 3 to 8 ring carbon atoms, several processes for the preparation of the new substances and their use as herbicides.

Description

The present invention relates to new substituted carboxylic acid anilides, several processes for their preparation and their use as herbicides.

It is already known that certain carboxanilides have herbicidal properties (cf. R. Wegler "Chemistry of Plant Protection Products and Pest Control" Vol. 2, pages 311-314, Springer-Verlag, Berlin 1970). For example, propionic acid 3,4-dichloroanilide can be used to control weeds. The effect of this compound is good, but some weeds are not always fully detected when small amounts are applied. In addition, the selectivity also leaves something to be desired in some cases.

It is also known that numerous pyrimidinyl-2-ethers and thioethers are suitable as herbicides (cf. JP-OS 9 474/1967, US Pat. Nos. 3, 126, 271 and US Pat. Nos. 3, 250, 775). For example, the 2-phenoxy-4,6-dimethyl-pyrimidine and the 2- (4-chloro-benzylmer- capto) -4,6-dimethyl-pyrimidine can be used to control weeds. However, the herbicidal potency of these substances is not always sufficient.

It is also known that lower acyl derivatives of 4-pyridyloxy (or thio) anilines have herbicidal properties (cf. DE-OS 2, 501, 648, JP-OS 55-122 763 and JP-OS 56-123 970) . In addition, herbicidally active acyl derivatives of 4-pyrimidyloxy-anilines are known which are substituted by halogen or trifluoromethyl in the 5-position of the pyrimidyl radical, but do not contain any substituents in positions 4 and 6 (cf. JP-OS 56-029 576) . However, the effectiveness of these substances is not always satisfactory for practical purposes.

in welcher

• X für Sauerstoff oder Schwefel steht,
• R¹ für Wasserstoff, Halogen, Alkyl mit 1 bis 6 Kohlenstoffatomen, Trifluormethyl, gegebenenfalls substituiertes Phenyl, Alkoxy mit 1 bis 6 Kohlenstoffatomen oder Alkylmercapto mit 1 bis 6 Kohlenstoffatomen steht,
• _R ² für Halogen oder Methyl steht,
• n für 0,1 oder 2 steht,
• R³ für Wasserstoff, Halogen, gegebenenfalls substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen, gegebenenfalls substituiertes Aryl, gegebenenfalls substituiertes Aralkyl oder für die Reste -OR⁶ oder -SO_m-R⁶ steht, wobei
• R⁶ für gegebenenfalls substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen oder für gegebenenfalls substituiertes Aryl steht und
• m für 0,1 oder 2 steht,
  und
• _R ⁴ und _R ⁵ unabhängig voneinander für Halogen oder gegebenenfalls substituiertes Alkyl mit 1 bis 6 Kohlenstoffatomen stehen oder
• _R ⁴ und _R ⁵ gemeinsam mit dem angrenzenden Kohlenstoffatom für einen gegebenenfalls substituierten, gesättigten oder ungesättigten carbocyclischen Ring mit 3 bis 8 Ring-Kohlenstoffatomen stehen,

gefunden.There have now been new substituted carboxanilides of the formula

in which

• X represents oxygen or sulfur,
• R ^{1 represents} hydrogen, halogen, alkyl having 1 to 6 carbon atoms, trifluoromethyl, optionally substituted phenyl, alkoxy having 1 to 6 carbon atoms or alkyl mercapto having 1 to 6 carbon atoms,
• _R ^{2 represents} halogen or methyl,
• n represents 0.1 or 2,
• R ^{3 represents} hydrogen, halogen, optionally substituted alkyl having 1 to 6 carbon atoms, optionally substituted aryl, optionally substituted aralkyl or the radicals -OR ⁶ or -SO _m -R ⁶ , where
• R ^{6 represents} optionally substituted alkyl having 1 to 6 carbon atoms or optionally substituted aryl and
• m represents 0.1 or 2,
  and
• _R ⁴ and _R ⁵ independently of one another represent halogen or optionally substituted alkyl having 1 to 6 carbon atoms or
• _R ⁴ and _R ⁵ together with the adjacent carbon atom represent an optionally substituted, saturated or unsaturated carbocyclic ring having 3 to 8 ring carbon atoms,

found.

• a) Anilin-Derivate der Formel
  
  
  in welcher
  • R¹, R², X und n die oben angegebene Bedeutung haben,
    entweder
  • α) mit Säurehalogeniden der Formel
    
    
    in welcher
  • _R ³, _R ⁴ und _R ⁵ die oben angegebene Bedeutung haben
    und
  • Y für Halogen steht,
  
  gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt,
  oder
• ß) mit symmetrischen Carbonsäureanhydriden der Formel
  
  
  in welcher
  • _R ³,_R ⁴ und R⁵ die oben angegebene Bedeutung haben,
  • gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt,
    oder
  • mit asymmetrischen Säureanhydriden der Formel
    
    
    in welcher
  • _R ³,_R ⁴ und _R ⁵ die oben angegebene Bedeutung haben und
  • R für Alkyl mit 1 bis 4 Kohlenstoffatomen oder Phenyl steht,
  
  gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt,
  oder
• 
  ) mit Verbindungen der Formel
  
  
  in welcher
  • _R ³, _R ⁴ _un_{d R} ⁵ die oben angegebene Bedeutung haben,
  • gegebenenfalls in Gegenwart eines Verdünnungsmittels umsetzt,
  
  oder
• b) Pyrimidin-Derivate der Formel
  
  
  in welcher
  • R¹ die oben angegebene Bedeutung hat und
  • Hal für Halogen steht,
  • mit Acylanilin-Derivaten der Formel
    
    
    in welcher
  • R², R³, R⁴, R , X und n die oben angegebene Bedeutung haben,
  • in Gegenwart eines Verdünnungsmittels umsetzt.

It has also been found that substituted carboxylic acid anilides of the formula (I) are obtained if

• a) Aniline derivatives of the formula
  
  
  in which
  • R ¹ , R ² , X and n have the meaning given above,
    either
  • α) with acid halides of the formula
    
    
    in which
  • _R ³ , _R ⁴ and _R ^{5 have} the meaning given above
    and
  • Y represents halogen,
  
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
  or
• ß) with symmetrical carboxylic anhydrides of the formula
  
  
  in which
  • _R ³ , _R ⁴ and R ^{5 have} the meaning given above,
  • if appropriate in the presence of a diluent,
    or
  • with asymmetric acid anhydrides of the formula
    
    
    in which
  • _R ³ , _R ⁴ and _R ^{5 have} the meaning given above and
  • R represents alkyl having 1 to 4 carbon atoms or phenyl,
  
  if appropriate in the presence of a diluent,
  or
• 
  ) with compounds of the formula
  
  
  in which
  • _R ³ , _R ⁴ _{and R} ^{5 have} the meaning given above,
  • if appropriate in the presence of a diluent,
  
  or
• b) pyrimidine derivatives of the formula
  
  
  in which
  • R ^{1 has} the meaning given above and
  • Hal stands for halogen,
  • with acylaniline derivatives of the formula
    
    
    in which
  • R ² , R ³ , R ⁴ , R, X and n have the meaning given above,
  • in the presence of a diluent.

Finally, it was found that the new substituted carboxanilides of the formula (I) are notable for excellent herbicidal activity.

Surprisingly, the substituted carboxylic acid anilides of the formula (I) according to the invention have significantly better herbicidal properties than the constitutionally most similar previously known substances. Thus, the carboxylic acid anilides of the formula (I) according to the invention can be used much better for weed control than the 2-phenoxy-4,6-dimethyl-pyrimidine, which is a structurally similar previously known active ingredient of the same type of action.

The substituted carboxylic acid anilides according to the invention are generally defined by the formula (I). In this formula, X stands for oxygen or sulfur. The radical R ¹ preferably represents hydrogen, fluorine, chlorine, Bromine, straight-chain or branched alkyl having 1 to 4 carbon atoms, trifluoromethyl, phenyl optionally substituted by chlorine, trifluoromethyl and / or methyl, alkoxy having 1 to 4 carbon atoms or alkyl mercapto having 1 to 4 carbon atoms. R preferably represents chlorine, bromine or methyl. The index n preferably stands for 0 or 1. R ³ preferably stands for hydrogen, fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms optionally substituted by fluorine, chlorine and / or bromine, optionally with fluorine, chlorine, bromine, trifluoromethyl, Methoxy and / or methyl substituted phenyl, optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, methoxy and / or methyl or for the radicals -OR ⁶ or -SO -R ⁶ , where R is preferably for optionally by fluorine, chlorine and / or bromine-substituted alkyl having 1 to 4 carbon atoms or phenyl optionally substituted by fluorine, chlorine, bromine and / or alkyl having 1 to 4 carbon atoms and the index m being 0, 1 or 2. R ⁴ and R ⁵ independently of one another are preferably fluorine, chlorine, bromine or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine, chlorine and / or bromine. In addition, R ⁴ and R ⁵ , together with the adjacent carbon atom, preferably represent a saturated or unsaturated carbocyclic ring with 3 to 7 ring carbon atoms which is optionally substituted by fluorine, chlorine and / or alkyl having 1 to 4 carbon atoms.

• X für Sauerstoff oder Schwefel steht,
• R¹ für Wasserstoff, Alkyl mit 1 bis 4 Kohlenstoffatomen, Alkoxy mit 1 bis 4 Kohlenstoffatomen oder Trifluormethyl steht,
• _R ² für Chlor, Brom oder Methyl steht,
• n für 0 oder 1 steht,
• _R ³ für Fluor, Chlor, Brom, gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 kohlenstoffatomen, gegebenenfalls durch Fluor, Chlor und/oder Methyl substituiertes Phenyl, gegebenenfalls durch Fluor, Chlor und/oder Methyl substituiertes Benzyl oder für die Reste -OR⁶ oder -SO_m R⁶ steht, worin
• R⁶ für gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen oder für gegebenenfalls durch Fluor, Chlor und/ oder Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Phenyl steht und
• m für 0, 1 oder 2 steht,
  und
• _R ⁴ und R⁵ unabhängig voneinander für Fluor, Chlor oder gegebenenfalls durch Fluor und/oder Chlor substituiertes Alkyl mit 1 bis 4 Kohlenstoffatomen stehen
  oder
• _R ⁴ und R⁵ gemeinsam mit dem angrenzenden Kohlenstoffatom für einen gegebenenfalls durch Fluor, Chlor, Methyl, Ethyl, n-Propyl, iso-Propyl, n-Butyl, isoButyl, sek.-Butyl und/oder tert.-Butyl substituierten gesättigten oder ungesättigten carbocyclischen Ring mit 3 bis 7 Ring-Kohlenstoffatomen stehen.

A particularly preferred group of the invention Substances are those substituted carboxanilides of the formula (I) in which

• X represents oxygen or sulfur,
• R ^{1 represents} hydrogen, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms or trifluoromethyl,
• _R ^{2 represents} chlorine, bromine or methyl,
• n represents 0 or 1,
• _R ³ for fluorine, chlorine, bromine, optionally substituted by fluorine and / or chlorine alkyl having 1 to 4 carbon atoms, optionally substituted by fluorine, chlorine and / or methyl phenyl, optionally substituted by fluorine, chlorine and / or methyl, or for the Radicals -OR ⁶ or -SO _m R ⁶ , wherein
• R ^{6 represents} optionally substituted by fluorine and / or chlorine alkyl having 1 to 4 carbon atoms or represents optionally substituted by fluorine, chlorine and / or alkyl having 1 to 4 carbon atoms and
• m represents 0, 1 or 2,
  and
• _R ⁴ and R ⁵ independently of one another represent fluorine, chlorine or alkyl having 1 to 4 carbon atoms which is optionally substituted by fluorine and / or chlorine
  or
• _R ⁴ and R ⁵ together with the adjacent carbon atom for a saturated or optionally substituted by fluorine, chlorine, methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and / or tert-butyl unsaturated carbocyclic ring having 3 to 7 ring carbon atoms.

The substances listed in Table 1 below may be mentioned as examples of substituted carboxanilides of the formula (I).

Table 1

If 4- (4,6-dimethyl-pyrimidyl-2-oxy) aniline and pivaloyl chloride are used as starting materials, the course of the process according to the invention (a, variant α) can be represented by the following formula:

Verwendet man 4-(4-Methyl-pyrimidyl-2-mercapto)-anilin und Isobuttersäureanhydrid als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (a, Variante ß) durch das folgende Formelschema wiedergegeben werden:

If 4- (4-methyl-pyrimidyl-2-mercapto) aniline and isobutyric anhydride are used as starting materials, the course of the process according to the invention (a, Vari ante ß) can be represented by the following formula:

If 4- (4,6-dimethyl-pyrimidyl-2-mercapto) aniline and α-methoxy-isobutyric acid-carbonic acid-ethyl ester-anhydride are used as starting materials, the course of the process (a, variant) according to the invention can be represented by the following formula will:

Verwendet man 4-(4,6-Dimethyl-pyrimidyl-2-oxy)-anilin und O-Pivaloyloxy-dicyclohexyl-isoharnstoff als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (a, Variante δ) durch das folgende Formelschema wiedergegeben werden:

If 4- (4,6-dimethyl-pyrimidyl-2-oxy) aniline and O-pivaloyloxydicyclohexyl isourea are used as starting materials, the course of the process according to the invention (a, variant δ) can be represented by the following formula:

Verwendet man 2-Chlor-4,6-dimethyl-pyrimidin und 4-Pivaloylamino-phenol als Ausgangsstoffe, so kann der Verlauf des erfindungsgemäßen Verfahrens (b) durch das folgende Formelschema wiedergegeben werden:

If 2-chloro-4,6-dimethyl-pyrimidine and 4-pivaloylamino-phenol are used as starting materials, the course of process (b) according to the invention can be represented by the following formula:

Die bei dem erfindungsgemäßen Verfahren (a) als Ausgangstoffe benötigten Anilin-Derivate sind durch die Formel (II) allgemein definiert. In dieser Formel haben R',R², X und n vorzugsweise diejenigen Bedeutungen, die bereits im Zusammenhang mit der Beschreibung der erfindungsgemäßen Stoffe der Formel (I) vorzugsweise für diese Reste bzw. diesen Index genannt wurden.

Formula (II) provides a general definition of the aniline derivatives required as starting materials in process (a) according to the invention. In this formula, R ', R ² , X and n preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals or this index.

• c) Pyrimidin-Derivate der Formel
  
  
  in welcher
  • R¹ und Hal die oben angegebene Bedeutung haben,
  • mit 4-Amino-(thio)-phenolen der Formel
    
    
    in welcher
  • _R ², _X und n die oben angegebene Bedeutung haben,
  • in Gegenwart eines Säurebindemittels sowie gegebenenfalls in Gegenwart eines Verdünnungsmittel umsetzt,
  
  oder
• d) 2-(4-Nitro-(thio)-Phenoxy)-pyrimidin-Derivate der Formel
  
  
  in welcher
  • R¹, R², X und n die oben angegebene Bedeutung haben,
  gegebenenfalls in Gegenwart eines Verdünnungsmittels nach üblichen Methoden reduziert.

Some of the aniline derivatives of the formula (II) are known. They can be made by

• c) pyrimidine derivatives of the formula
  
  
  in which
  • R ¹ and Hal have the meaning given above,
  • with 4-amino (thio) phenols of the formula
    
    
    in which
  • _R ² , _X and n have the meaning given above,
  • in the presence of an acid binder and optionally in the presence of a diluent,
  
  or
• d) 2- (4-nitro- (thio) phenoxy) pyrimidine derivatives of the formula
  
  
  in which
  • R ¹ , R ² , X and n have the meaning given above,
  optionally reduced in the presence of a diluent by customary methods.

Formula (IV) defines the pyrimidine derivatives required as starting materials in process (c) above. In this formula, R ¹ preferably has those meanings which have preferably been mentioned for this radical in connection with the description of the substances of the formula (I) according to the invention. Hal preferably represents fluorine, chlorine or bromine.

• 2-Chlor-4-methyl-pyrimidin
• 2-Brom-4-methyl-pyrimidin
• 2,4-Dichlor-6-methyl-pyrimidin
• 2-Chlor-4-methoxy-6-methylpyrimidin
• 2-Chlor-4-methylmercapto-6-methyl-pyrimidin
• 2-Chlor-4,6-dimethyl-pyrimidin
• 2-Fluor-4,6-dimethyl-pyrimidin
• 2-Chlor-4-methyl-6-propyl-pyrimidin
• 2-Chlor-4-methyl-6-isopropyl-pyrimidin
• 2-Chlor-4-methyl-6-trifluormethyl-pyrimidin
• 2-Chlor-4-methyl-6-phenyl-pyrimidin
• 2-Chlor-4-methyl-6-(4-chlor-phenyl)-pyrimidin
• 2-Chlor-4-methyl-6-(4-methyl-phenyl)-pyrimidin
• 2-Chlor-4-methyl-6-(3-trifluormethyl-phenyl)-pyrimidin

The following may be mentioned as examples of pyrimidine derivatives of the formula (IV):

• 2-chloro-4-methyl-pyrimidine
• 2-bromo-4-methyl-pyrimidine
• 2,4-dichloro-6-methyl-pyrimidine
• 2-chloro-4-methoxy-6-methylpyrimidine
• 2-chloro-4-methylmercapto-6-methyl-pyrimidine
• 2-chloro-4,6-dimethyl-pyrimidine
• 2-fluoro-4,6-dimethyl-pyrimidine
• 2-chloro-4-methyl-6-propyl-pyrimidine
• 2-chloro-4-methyl-6-isopropyl-pyrimidine
• 2-chloro-4-methyl-6-trifluoromethyl-pyrimidine
• 2-chloro-4-methyl-6-phenyl-pyrimidine
• 2-chloro-4-methyl-6- (4-chlorophenyl) pyrimidine
• 2-chloro-4-methyl-6- (4-methylphenyl) pyrimidine
• 2-chloro-4-methyl-6- (3-trifluoromethylphenyl) pyrimidine

The pyrimidine derivatives of the formula (IV) are known or can be prepared in a simple manner by methods known in principle. For example, pyrimidine derivatives of the formula (IV) are obtained by reacting 2-hydroxy-pyrimidine derivatives (dihydro-pyrimidone-2 derivatives) with inorganic acid halides, such as phosphorus oxychloride or phosphorus pentachloride, or else by reacting corresponding 2-amino-pyrimidine derivatives with nitrous acid in the presence of hydrohalic acids.

Formula (VI) defines the 4-amino (thio) phenols which are further required as starting materials in process (c). In this formula, R ² , X and n preferably have those meanings which have already been mentioned preferably in connection with the description of the substances of the formula (I) according to the invention for these radicals or for this index.

• 4-Amino-phenol
• 2-Chlor-4-amino-phenol
• 3-Chlor-4-amino-phenol
• 2,5-Dichlor-4-amino-phenol
• 2,6-Dichlor-4-amino-phenol
• 2-Methyl-4-amino-phenol
• 3-Methyl-4-amino-phenol
• 2-Chlor-5-methyl-4-amino-phenol
• 4-Amino-thiophenol
• 2-Chlor-4-amino-thiophenol
• 3-Chlor-4-amino-thiophenol
• 2-Methyl-4-amino-thiophenol
• 3-Methyl-4-amino-thiophenol

As examples of 4-amino (thio) phenols of the formula (VI) may be mentioned:

• 4-aminophenol
• 2-chloro-4-aminophenol
• 3-chloro-4-aminophenol
• 2,5-dichloro-4-aminophenol
• 2,6-dichloro-4-aminophenol
• 2-methyl-4-aminophenol
• 3-methyl-4-aminophenol
• 2-chloro-5-methyl-4-aminophenol
• 4-amino-thiophenol
• 2-chloro-4-aminothiophenol
• 3-chloro-4-aminothiophenol
• 2-methyl-4-aminothiophenol
• 3-methyl-4-aminothiophenol

The 4-amino (thio) phenols of the formula (VI) are known or can be prepared in a simple manner by methods known in principle.

All acid acceptors that can usually be used for such reactions can be used as acid binders when carrying out process (c). Alkali and alkaline earth oxides, hydroxides and carbonates such as sodium hydroxide, potassium hydroxide, calcium oxide, sodium carbonate and potassium carbonate are preferably usable, furthermore alkali alcoholates, amides and hydrides such as sodium methylate, sodium ethylate, potassium tert. butylate, sodium amide and sodium hydride.

All customary inert organic solvents can be used as diluents when carrying out process (c). Hydrocarbons such as gasoline, toluene and xylene, ethers such as dioxane, glycol dimethyl ether and diglycol dimethyl ether, furthermore nitriles such as acetonitrile, and also strongly polar solvents such as dimethyl sulfoxide, sulfolane and dimethylformamide are preferred.

The reaction temperatures can be varied within a substantial range when carrying out process (c). In general, temperatures between 0 ° C and 200 ° C, preferably between 50 ° C and 150 ° C.

The reaction according to process (c) is generally carried out under normal pressure.

When carrying out process (c), the starting materials of the formulas (IV) and (VI) are generally reacted in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess. The processing takes place according to usual methods.

Formula (VII) defines the 2- (4-nitro (thio) phenoxy) pyrimidine derivatives required as starting materials in process (d). In this formula, R ¹ , R ² , X and n preferably have those meanings which are already in connection with the description the substances of the formula (I) according to the invention were preferably mentioned for these radicals or for this index.

in welcher

• R und Hal die oben angegebene Bedeutung haben,
• mit 4-Nitro-(thio)-phenolen der Formel
  
  
  in welcher
• _R ², _X und n die oben angegebene Bedeutung haben,

in Gegenwart eines Säurebindemittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels bei Temperaturen zwischen 0°C und 200°C, vorzugsweise zwischen 50°C und 150°C, umsetzt. Als Säurebindemittel und Verdünnungsmittel kommen hierbei vorzugsweise diejenigen Stoffe in Betracht, die bereits im Zusammenhang mit dem Verfahren (c) als vorzugsweise verwendbare Säureakzeptoren und Solventien genannt wurden.The compounds of the formula (VII) are known or can be prepared in a simple manner by methods known in principle. Compounds of formula (VII) are thus obtained, for example, by using pyrimidine derivatives of the formula

in which

• R and Hal have the meaning given above,
• with 4-nitro (thio) phenols of the formula
  
  
  in which
• _R ² , _X and n have the meaning given above,

in the presence of an acid binder and optionally in the presence of a diluent at temperatures between 0 ° C. and 200 ° C., preferably between 50 ° C. and 150 ° C. As an acid binder and diluent means here are preferably those substances which have already been mentioned in connection with process (c) as preferably usable acid acceptors and solvents.

Suitable as reducing agents in process (d) are all those substances which are usually used for the reduction of aromatic nitro compounds. Elemental metals, such as iron, zinc and tin, are preferably usable, furthermore metal compounds in lower valence levels, such as iron (II) and tin (II) salts, and also non-metal compounds in low valence levels, such as, for example, salts of hydrogen sulfide, alkali metal sulfites and alkalidithionites. Otherwise, the reduction can also be carried out by catalytic hydrogenation with hydrogen in the presence of a catalyst, such as Raney nickel.

Suitable diluents in process (d) are all customary organic solvents suitable for such reductions. The reaction temperatures can be varied within a substantial range. They correspond to the temperatures used in analog reactions.

The reduction is carried out according to process (d) and the reaction mixture obtained is worked up using customary methods.

The process (a, variant α) Acid halides required as reaction components are clearly defined by the formula (III a). In this formula, R ³ , R ⁴ and R ⁵ preferably have those meanings which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention. Y preferably represents fluorine, chlorine and bromine.

• Trichloressigsäure
• Trifluoressigsäure
• α,α-Dichlorpropionsäure
• Isobuttersäure
• α -Chlor-isobuttersäure
• α-Brom-isobuttersäure
• α-Methoxy-isobuttersäure
• α-Phenoxy-isobuttersäure
• d-(4-Chlor-phenoxy)-isobuttersäure
• α-(2-Methyl-4-chlor-phenoxy)-isobuttersäure
• α-Methylmercapto-isobuttersäure
• α-Methylsulfonyl-isobuttersäure
• α-Methyl-buttersäure
• Pivalinsäure
• ß-Fluor-pivalinsäure
• ß-Chlor-pivalinsäure
• ß,ß'-Difluor-pivalinsäure
• ß,ß'-Dichlor-pivalinsäure
• β,β'β"-Trifluor-pivalinsäure
• ß,ß'ß"-Trichlor-pivalinsäure
• α,α-Dimethyl-valeriansäure
• α-Methyl-α-ethyl-buttersäure
• α,α-Dimethyl-phenylessigsäure
• α,α-Dimethyl-(4-chlor-phenyl)-essigsäure
• α,α-Dimethyl-(3,4-dichlor-phenyl)-essigsäure
• α,α-Dimethyl-(3-trifluormethyl-phenyl)-essigsäure
• α-Benzyl-isobuttersäure
• o(--(4-Chlor-benzyl)-isobuttersäure
• α-(4-Methoxy-benzyl)-isobuttersäure
• Cyclopropan-carbonsäure
• 1-Methyl-cyclopropan-carbonsäure
• 2,2-Dichlor-1-methyl-cyclopropan-carbonsäure Cyclopentan-carbonsäure
• 1-Methyl-cyclopentan-carbonsäure
• Cyclohexan-carbonsäure
• 1-Methyl-cyclohexan-carbonsäure
• 1-Methyl-4-isopropyl-cyclohexan-carbonsäure

The chlorides of the following acids may be mentioned as examples of acid halides of the formula (III a):

• Trichloroacetic acid
• Trifluoroacetic acid
• α, α-dichloropropionic acid
• Isobutyric acid
• α-chloro-isobutyric acid
• α-bromo-isobutyric acid
• α-methoxy-isobutyric acid
• α-phenoxy-isobutyric acid
• d- (4-chlorophenoxy) isobutyric acid
• α- (2-Methyl-4-chlorophenoxy) isobutyric acid
• α-methylmercapto isobutyric acid
• α-methylsulfonyl isobutyric acid
• α-methyl butyric acid
• Pivalic acid
• ß-fluoro-pivalic acid
• ß-chloro-pivalic acid
• ß, ß'-difluoropivalic acid
• ß, ß'-dichloropivalic acid
• β, β'β "-trifluoropivalic acid
• ß, ß'ß "-Trichlor-pivalic acid
• α, α-dimethylvaleric acid
• α-methyl-α-ethyl-butyric acid
• α, α-dimethyl-phenylacetic acid
• α, α-Dimethyl- (4-chlorophenyl) acetic acid
• α, α-dimethyl- (3,4-dichlorophenyl) acetic acid
• α, α-Dimethyl- (3-trifluoromethyl-phenyl) acetic acid
• α-benzyl isobutyric acid
• o (- (4-chlorobenzyl) isobutyric acid
• α- (4-methoxy-benzyl) isobutyric acid
• Cyclopropane carboxylic acid
• 1-methyl-cyclopropane-carboxylic acid
• 2,2-dichloro-1-methyl-cyclopropane-carboxylic acid cyclopentane-carboxylic acid
• 1-methyl-cyclopentane carboxylic acid
• Cyclohexane carboxylic acid
• 1-methyl-cyclohexane-carboxylic acid
• 1-methyl-4-isopropyl-cyclohexane-carboxylic acid

The acid halides of the formula (III a) are known or can be prepared in a simple manner by methods known in principle.

Suitable acid binders for the reaction according to process (a, variant α) are all customary acid acceptors. Tertiary amines, such as triethylamine, pyridine and N, N-dimethylaniline, furthermore alkaline earth metal oxides, such as magnesium and calcium oxide, and also alkali metal and alkaline earth metal carbonates, such as sodium carbonate, potassium carbonate and calcium carbonate, are preferably usable. It is also possible, to use the respective aniline derivatives of the formula (II) at the same time as acid binders. For this purpose, the aniline compound in question must then be used at least in such an amount that the hydrogen halide released can be bound.

Diluents which can be used in process (a, Variantedl) according to the invention are all solvents which are inert to acid halides. Hydrocarbons such as gasoline, benzene, toluene, xylene and tetralin are preferably usable, furthermore halogenated hydrocarbons such as methylene chloride, chloroform, carbon tetrachloride, chlorobenzene and o-dichlorobenzene, also ketones such as acetone and methyl isopropyl ketone, furthermore ethers such as diethyl ether, tetrahydrofuran and Dioxane, moreover carboxylic acid esters, such as ethyl acetate, and also strongly polar solvents, such as dimethyl sulfoxide and sulfolane. If the hydrolysis stability of the acid halide permits, the reaction can also be carried out in the presence of water.

The reaction temperatures can be varied within a substantial range when carrying out the process (a, Variantedj). If one works without solvents and acid binders, the procedure is generally such that the components are initially at temperatures between -20 ° C. and +20 ° C can react and then heated to temperatures between 70 and 200 ° C. If one works in the presence of a diluent and an acid binder, the are Reaction temperatures in general between -20 ° C and + 100 ° C, preferably between 0 ° C and 50 ° C.

The process (a, variant α) according to the invention is generally carried out under normal pressure.

When carrying out process (a, variant J) according to the invention, the starting materials of the formulas (II) and (III a) are generally used in approximately equivalent amounts. However, it is also possible to use one or the other component in a larger excess. The processing is then carried out using customary methods. The general procedure is to remove precipitated salts and to concentrate the remaining reaction mixture by stripping off the diluent. If one works in the presence of water or of water-miscible solvents, the procedure can also be such that the reaction mixture is diluted with water, the resulting mixture is suctioned off or extracted with a water-immiscible organic solvent, the organic phase is washed, concentrated and the the remaining residue may be subjected to customary cleaning procedures.

The symmetrical carboxylic acid anhydrides required as reaction components in the process (a, variant β) according to the invention are clearly defined by the formula (III b). In this formula, _R ³ , _R ⁴ and _R ⁵ preferably have those meanings which are already in connection with the description of the invention Substances of formula (I) were preferably mentioned for these radicals.

The symmetrical carboxylic anhydrides of the formula (III b) are known or can be prepared in a simple manner by methods known in principle.

The diluents which can be used in carrying out the process (a, variant β) are preferably those diluents which are also preferred in the process (a, variant δ). Otherwise, an excess carboxylic acid anhydride of the formula (III b) can also act as a diluent.

The reaction temperatures can also be varied within a substantial range in the process according to the invention (a, variant β). In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 and 100 ° C.

The process (a, variant β) according to the invention is generally carried out under normal pressure.

When carrying out the process (a, variant β) according to the invention, the starting materials of the formulas (II) and (III b) are generally used in approximately equivalent amounts. However, it is also possible to use the carboxylic anhydride in a larger excess. The processing takes place according to usual methods.

In general, the procedure is to remove diluent and excess carboxylic acid anhydride and the carboxylic acid formed by distillation or by washing with an organic solvent or with water.

The asymmetric acid anhydrides required as reaction components in the process (a, variant) according to the invention are clearly defined by the formula (III c). In this formula, R ³ , _R ⁴ and _R ⁵ preferably have those meanings which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention. R preferably represents alkyl having 1 or 2 carbon atoms or phenyl.

in welcher

• _R ³, _R ⁴ und _R ⁵ die oben angegebene Bedeutung haben,
• mit Kohlensäure-ester-chloriden der Formel
  
  
  in welcher
• R die oben angegebene Bedeutung hat,

in Gegenwart eines Verdünnungsmittels, wie zum Beispiel Methylenchlorid, und in Gegenwart eines Säurebindemittels, wie zum Beispiel Triethylamin, bei Temperaturen zwischen -20°C und +100°C, vorzugsweise zwischen 0 und 50°C, umsetzt. Die asymmetrischen Säureanhydride der Formel (III c) werden im allgemeinen nicht in reiner Form isoliert, sondern in der anfallenden Form, gegebenenfalls nach vorheriger Entfernung von Verdünnungsmittel und/ oder Salzen, weiter verwendet.The asymmetric acid anhydrides of the formula (III c) are known or can be prepared in a simple manner by methods known in principle. Thus, compounds of formula (III c) are obtained by carboxylic acids of the formula

in which

• _R ³ , _R ⁴ and _R ^{5 have} the meaning given above,
• with carbonic acid ester chlorides of the formula
  
  
  in which
• R has the meaning given above,

in the presence of a diluent, such as methylene chloride, and in the presence of an acid binder, such as triethylamine, at temperatures between -20 ° C and + 100 ° C, preferably between 0 and 50 ° C. The asymmetric acid anhydrides of the formula (III c) are generally not isolated in pure form, but are used further in the form obtained, if appropriate after removing diluent and / or salts beforehand.

The diluents which can be used in carrying out the process (a, variant) according to the invention are preferably those diluents which are also preferred in the process (a, variant α). In addition, excess acid anhydride of the formula (III c) can also act as a diluent.

The reaction temperatures can also be varied within a substantial range in the process (a, variant f) according to the invention. In general one works with temperature fittings between -20 ° C and + 150 ° C, preferably between 0 and 100 ° C.

The process (a, variant f) according to the invention is generally carried out under normal pressure.

When carrying out process (a, variant δ) according to the invention, the starting materials of the formulas (II) and (III c) are generally used in approximately equivalent amounts. However, it is also possible to use the acid anhydride in a larger excess. The processing takes place according to usual methods.

The compounds required as reaction components in the process (a, variant) according to the invention are clearly defined by the formula (III d). In this formula, R ³ , R ⁴ and R ⁵ preferably have those meanings which have already been mentioned for these radicals in connection with the description of the substances of the formula (I) according to the invention.

in welcher

• _R ³, _R ⁴ und R die oben angegebene Bedeutung haben,

mit Dicyclohexylcarbodiimid der Formel

umsetzt.The compounds of the formula (III d) are known or can be prepared in a simple manner by processes which are known in principle. Thus, compounds of formula (III d) are obtained by carboxylic acids of the formula

in which

• _R ³ , _R ⁴ and R have the meaning given above,

with dicyclohexylcarbodiimide of the formula

implements.

Diluents which can be used when carrying out process (a, variant δ) according to the invention are preferably those diluents which are also preferred in process (a, variant α).

The reaction temperatures can also be varied within a substantial range in the process (a, variant) according to the invention. In general, temperatures between -20 ° C and + 150 ° C, preferably between 0 and 100 ° C.

The process (a, variant δ) according to the invention is generally carried out under normal pressure.

When carrying out process (a, variant δ) according to the invention, the starting materials of the formulas (II) and (III d) are generally used in approximately equivalent amounts. The processing takes place according to usual methods.

The pyrimidine derivatives required as starting materials in process (b) according to the invention have already been dealt with in connection with the description of process (c).

Formula (V) clearly defines the acylaniline derivatives required as starting materials in process (b) according to the invention. In this formula, _R ² , _R ³ , _R ⁴ , _R ⁵ , _X and n preferably have those meanings which have already been mentioned in connection with the description of the substances of the formula (I), preferably for these radicals or for this index.

in welcher

• R², _X und n die oben angegebene Bedeutung haben,
  mit Säurehalogeniden der Formel
  
  
  in welcher
• _R ³, _R ⁴, _R ⁵ und _Y die oben angegebene Bedeutung haben,

gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt. Die Reaktionsbedingungen entsprechen dabei denjenigen, die auch bei der Durchführung des Verfahrens (a, VariantecL) angewandt werden.The compounds of the formula (V) are known or can be prepared in a simple manner by methods known in principle. For example, acylaniline derivatives of the formula (V) are obtained by adding 4-amino (thio) phenols of the formula

in which

• R ² , _X and n have the meaning given above,
  with acid halides of the formula
  
  
  in which
• _R ³ , _R ⁴ , _R ⁵ and _{Y have} the meaning given above,

if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder. The reaction conditions correspond to those which are also used when carrying out process (a, variant cL).

All customary acid acceptors can be used as acid binders when carrying out process (b) according to the invention. Alkali metal and alkaline earth metal oxides, hydroxides and carbonates, such as sodium hydroxide, potassium hydroxide, magnesium oxide, calcium oxide, sodium carbonate, potassium carbonate and calcium carbonate, furthermore alkali metal and alkaline earth metal amides and hydrides, such as sodium amide, sodium hydride and calcium hydride, and also also are preferably usable Alkali metal alcoholates, such as sodium methylate, sodium ethylate and potassium tert-butoxide.

All customary inert organic solvents can be used as diluents in process (b) according to the invention. Hydrocarbons such as toluene and xylene are preferably usable, furthermore ethers such as dibutyl ether, tetrahydrofuran, dioxane, glycol dimethyl ether and diglycol dimethyl ether, also nitriles such as acetonitrile and propionitrile and also polar ones Solvents such as nitrobenzene, dimethyl sulfoxide, sulfolane, dimethylformamide and N-methyl-pyrrolidone.

The reaction temperatures can be varied within a substantial range when carrying out process (b) according to the invention. In general, temperatures between 0 and 200 ° C, preferably between 50 and 150 ° C.

Process (b) according to the invention is generally carried out under normal pressure.

When carrying out process (b) according to the invention, the reaction components of the formulas (IV) and (V) are generally employed in approximately equimolar amounts. However, it is also possible to use one or the other component in a larger excess. In addition, an equimolar amount of acid-binding agent is generally also used. However, it may also be advantageous to add the acid binder in an excess of up to one molar. In particular, the general procedure is to add the acid-binding agent to a mixture of the reaction components in a suitable diluent. However, one can also proceed in such a way that a salt is first produced from the acylaniline derivative of the formula (V) and the acid binder and this is then reacted with a pyrimidine derivative of the formula (IV). Furthermore, it is also possible to use the acylaniline derivative of the formula (V) to produce a salt separately from an acid binder, then to isolate it and then to react it with a pyrimidine derivative of the formula (IV) in the presence of a suitable diluent without further addition of an acid binder. - The processing is carried out according to the usual methods.

The active compounds according to the invention can be used as defoliants, desiccants, haulm killers and in particular as weed killers. Weeds in the broadest sense are understood to mean all plants that grow up in places where they are undesirable. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.

• Dikotyle Unkräuter der Gattungen: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
• Dikotyle Kulturen der Gattungen: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
• Monokotyle Unkräuter der Gattungen: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
• Monokotyle Kulturen der Gattungen: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Ananas, Asparagus, Allium.

The active compounds according to the invention can be used, for example, in the following plants:

• Dicotyledon weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsorus, Carduusanum, Sonuanum , Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea.
• Dicotyledon cultures of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.
• Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Iochasemirumum, Scalumum, Scalumumum , Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.
• Monocot cultures of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means restricted to these genera, but extends in the same way to other plants.

Depending on the concentration, the compounds are suitable for total weed control, e.g. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the compounds for weed control in permanent crops, e.g. Forestry, ornamental trees, fruit, wine, citrus, nut, banana, coffee, tea, rubber, oil palm, cocoa, berry fruit and hop plants and for selective weed control in annual crops.

The active compounds according to the invention are particularly suitable for the selective control of mono- and dicotyledon weeds in monocotyledon crops, such as, for example, maize and cereals.

The active compounds according to the invention also have a strong microbicidal action and can be used practically to combat unwanted microorganisms. The active ingredients are suitable for use as pesticides.

Fungicidal agents in crop protection are used to control Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

The fact that the active compounds are well tolerated by plants in the concentrations required to combat plant diseases permits treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil.

The active compounds according to the invention can be used with particular advantage for combating Pyricularia oryzae in rice, against botrytis and for combating bean rust.

Otherwise, the substances according to the invention are also distinguished by an insecticidal activity. They have a good root systemic effectiveness. The active ingredients can be converted into the customary formulations, such as solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension emulsion concentrates, active ingredient-impregnated natural and synthetic substances and very fine encapsulations in polymeric substances.

These formulations are made in a known manner, e.g. by mixing the active ingredients with extenders, that is to say liquid solvents and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents.

If water is used as an extender, e.g. organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, mineral and vegetable oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water.

• z. B. Ammoniumsalze und natürliche Gesteinsmehle, wie Kaoline, Tonerden, Talkum, Kreide, Quarz, Attapulgit, Montmorillonit oder Diatomeenerde und synthetische Gesteinsmehle, wie hochdisperse Kieselsäure, Aluminiumoxid und Silikate, als feste Trägerstoffe für Granulate kommen in Frage: z.B. gebrochene und fraktionierte natürliche Gesteine wie Calcit, Marmor, Bims, Sepiolith, Dolomit sowie synthetische Granulate aus anorganischen und organischen Mehlen sowie Granulate aus organischem Material wie Sägemehl, Kokosnußschalen, Maiskolben und Tabakstengeln; als Emulgier- und/oder schaumerzeugende Mittel kommen in Frage: z.B. nichtionogene und anionische Emulgatoren, wie Polyoxyethylen-Fettsäure-Ester, Polyoxyethylen-FettalkoholEther, z.B. Alkylaryl-polyglykolether, Alkylsulfonate, Alkylsulfate, Arylsulfonate sowie Eiweißhydrolysate; als Dispergiermittel kommen in Frage: z.B. Lignin-Sulfitablaugen und Methylcellulose.

The following are suitable as solid carriers:

• e.g. B. ammonium salts and natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock flours, such as highly disperse silica, aluminum oxide and silicates, are suitable as solid carriers for granules: e.g. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; Suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates; The following may be used as dispersants: for example lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospholipids, such as cephalins and lecithins and synthetic phospholipids, can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active compound, preferably between 0.5 and 90%.

The active compounds according to the invention, as such or in their formulations, can also be used for weed control in a mixture with known herbicides, finished formulations or tank mixes being possible.

Known herbicides such as z. B. N- (2-Benzothiazolyl) -N, N'-dimethylurea, 3- (3-chloro-4-methylphenyl) -1,1-dimethylurea, 3- (4-isopropylphenyl) -1,1-dimethylurea , 4-amino-6- (1,1-dimethylethyl) -3-methylthio-1,2,4-triazin-5 (4H) -one, 4-amino-6- (1,1-dimethyl-ethyl) - 3-ethylthio-1,2,4-triazin-5 (4H) -one, 1-amino-6-ethylthio-3- (2,2-dimethylpropyl) -1,3,5-triazine-2,4- ( 1H, 3H) -dione, 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5 (4H) -one, 2-chloro-4-ethylamino-6-isopropylamino-1, 3,5-triazine, the R-enantiomer of 2-L4- (3,5-dichloropyridine-2-oxy) -phenox _{Y /} -propionic acid (trimethylsilyl) -methyl ester, the R-enantiomer of 2- [4th - (3,5-dichloropyridyl-2-oxy) phenoxy] propionic acid (2-benzyloxy) ethyl ester, 2,4-dichlorophenoxyacetic acid, 2- (2,4-dichlorophenoxy) propionic acid, 4-chloro-2- methyl-phenoxy-acetic acid, 2- (2-methyl-4-chlorophenoxy) propionic acid, 3,5-diiodo-4-hydroxy-benzonitrile, 3,5-dibromo-4-hydroxy-benzonitrile as well as diphenyl ether and phenylpyridazine, such as pyridates. Surprisingly, some mixtures also show a synergistic effect.

A mixture with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellants, plant nutrients and agents which improve soil structure, is also possible.

The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, suspensions, emulsions, powders, pastes and granules. The application happens in the usual way, e.g. B. by pouring, spraying, spraying, scattering.

When used as herbicides, the active compounds according to the invention can be applied both before and after emergence of the plants. They can also be worked into the soil before sowing.

The amount of active ingredient used can vary over a wide range when the substances according to the invention are used as herbicides. It essentially depends on the type of effect desired. In general, the application rates are between 0.01 and 10 kg of active ingredient per hectare of soil, preferably between 0.05 and 5 kg per ha.

When using the substances according to the invention as fungicides, the application rate can be varied within a substantial range depending on the type of application. The active substance concentrations in the treatment of parts of plants in the use forms are generally between 1 and 0.0001% by weight, preferably between 0.5 and 0.001% by weight. When treating seeds, in general Active ingredient amounts of 0.001 to 50 g per kg of seed, preferably 0.01 to 10 g, are required. When treating the soil, active ingredient concentrations of 0.00001 to 0.1% by weight, preferably 0.0001 to 0.02%, are required at the site of action.

The preparation and use of the active compounds according to the invention can be seen from the examples below.

Manufacturing examples example 1

(Method a)

21.5 g (0.1 mol) of 2- (4-aminophenoxy) -4,6-dimethyl-pyrimidine were dissolved in 150 ml of tetrahydrofuran. 10.1 g (0.1 mol) of triethylamine were added and 12 g (0.1 mol) of pivaloyl chloride were then added dropwise at a temperature of 10 to 15 ° C. with stirring. The mixture was stirred at room temperature for 2 hours. The mixture was then worked up by sucking off the solid product which had separated off and evaporating the filtrate under reduced pressure. There remained 27.5 g (92% of theory) of 2- (4-pivaloylamino-phenoxy) -4,6-dimethyl-pyrimidine in the form of a solid product.

Melting point: 190-191 ° C (after recrystallization from ethyl acetate)

Example 2

11.8 g (0.1 mol) of o6-methoxy-isobutyric acid were dissolved in 150 ml of tetrahydrofuran, and 10.1 g (0.1 mol) of triethylamine were added. For this, 10.85 g (0.1 mol) of ethyl carbonate chloride were added dropwise at 10-15 ° C. with stirring. The mixture was stirred for 2 hours at room temperature and then 23.1 g (0.1 mol) of 2- (4-aminophenylmercapto) -4,6-dimethyl-pyrimidine were added in portions. The mixture was stirred at room temperature for 1 hour and refluxed for a further 2 hours. The reaction mixture was cooled and then stirred into 1 liter of water slightly acidified with hydrochloric acid. The deposited crystals were suction filtered, washed with water and air dried. 27.4 g (83% of theory) of 2- (4- (α-methoxy-isobutyrylamino) phenylmercapto) -4,6-dimethyl-pyrimidine were obtained.

Melting point: 123 - 125 ° C (after recrystallization from white spirit)

Example 3

(Method b)

22.8 g (0.1 mol) of 3-chloro-4-pivaloylamino-phenol were dissolved in 150 ml of dimethyl sulfoxide. 5.6 g (0.1 mol) were added in portions at room temperature with stirring powdered potassium hydroxide. The mixture was stirred at room temperature for 30 minutes and then 14.25 g (0.1 mol) of 2-chloro-4,6-dimethyl-pyrimidine were added in portions. The mixture was heated to 120 ° C. within one hour and stirred at this temperature for a further 5 hours. The mixture was then cooled and poured into 1 liter of water. The crystals were suctioned off and air dried. 25.5 g (76.5% of theory) of 2- (3-chloro-4-pivaloylamino-phenoxy) -4,6-dimethylpyrimidine were obtained.

Melting point: 83 - 85 ° C

According to the methods given in the preceding examples and in the description, the substances of the formula (I) listed in the following table were also prepared.

Table 2

Manufacture of raw materials Example 75

(Method d)

24.5 g (0.1 mol) of 2- (4-nitro-phenoxy) -4,6-dimethylpyrimidine were dissolved in 150 ml of dioxane and hydrogenated in the presence of Raney nickel under a pressure of 50 bar at a Temperature between 20 and 50 ° C exhaustively hydrogenated. The catalyst was then suction filtered and the filtrate was evaporated under reduced pressure. 20.4 g (95% of theory) of 2- (4-aminophenoxy) -4,6-dimethylpyrimidine were obtained in the form of a solid substance.

Melting point: 170 - 171 ° C (after recrystallization from ethyl acetate)

The substances of the formula (II) listed in the following examples were also prepared by the method given in Example ₇₅ .

Example 76

Melting point: 170 - 172 ° C (after recrystallization from ethyl acetate)

Example 77

Schmelzpunkt: 134 - 135°C (nach Umkristallisation aus Toluol)

Melting point: 134 - 135 ° C (after recrystallization from toluene)

Example 78

(Method c) ^-

109 g (1 mol) of 4-aminophenol were dissolved in 500 ml of dimethyl sulfoxide. After the addition of 56 g (1 mol) of powdered potassium hydroxide, the mixture was stirred for 30 minutes at room temperature and then 143 g (1 mol) of 2-chloro-4,6-dimethyl-pyrimidine were added in portions.

The mixture was heated at 100 ° C for 5 hours, cooled and then stirred into 3 liters of water. The crystals were filtered off, washed several times with water and dried. 119 g (55.3% of theory) of 2- (4-amino-phenoxy) -4,6-dimethyl-pyrimidine were obtained.

Melting point: 170 - 171 ° C (after recrystallization from ethanol)

The substances of the formula (II) listed in the following examples were also prepared by the method given in Example 78.

Example 79

Schmelzpunkt: 226 - 228°C (nach Umkristallisation aus Ethanol)

Melting point: 226 - 228 ° C (after recrystallization from ethanol)

Example 30

Schmelzpunkt: 167 - 168°C (nach Umkristallisation aus Toluol)

Melting point: 167-168 ° C (after recrystallization from toluene)

Example 81

Schmelzpunkt: 73-74°C (nach Umkristallisation aus Tetrachlormethan)

Melting point: 73-74 ° C (after recrystallization from carbon tetrachloride)

Example 82

27,8 g (0,2 Mol) 4-Nitro-phenol wurden in 100 ml Dimethylsulfoxid gelöst. Nach Zugabe von 11,2 g (0,2 Mol) pulverisiertem Kaliumhydroxid rührte man das Gemisch 30 Minuten bei Raumtemperatur und gab dann 28,5 g (0,2 Mol) 2-Chlor-4,6-dimethyl-pyrimidin hinzu. Die Mischung wurde 6 Stunden auf 120°C erhitzt, dann abgekühlt, mit 1 Liter Wasser verrührt und abgesaugt. Die abgesaugten Kristalle wurden an der Luft getrocknet. Man erhielt 38 g (77,5 % der Theorie) 2-(4-Nitrophenoxy)-4,6-dimethyl-pyrimidin.

27.8 g (0.2 mol) of 4-nitro-phenol were dissolved in 100 ml of dimethyl sulfoxide. After the addition of 11.2 g (0.2 mol) of powdered potassium hydroxide, the mixture was stirred for 30 minutes at room temperature and then 28.5 g (0.2 mol) of 2-chloro-4,6-dimethyl-pyrimidine were added. The mixture was heated to 120 ° C. for 6 hours, then cooled, stirred with 1 liter of water and suction filtered. The extracted crystals were air dried. 38 g (77.5% of theory) of 2- (4-nitrophenoxy) -4,6-dimethyl-pyrimidine were obtained.

Melting point: 108-110 ° C.

Example 83

109 g (1 Mol) 4-Amino-phenol und 101 g Triethylamin wurden in 700 ml Tetrahydrofuran gelöst. Hierzu tropfte man bei 10 - 15°C unter Rühren 120,5 g (1 Mol) Pivalsäurechlorid. Die Mischung wurde 2 Stunden bei Raumtemperatur nachgerührt, und dann in 3 Liter Wasser eingegossen. Die abgeschiedenen Kristalle wurden abgesaugt und an der Luft getrocknet. Man erhielt 165 g (85,5 % der Theorie) 4-Pivaloylamino-phenol.

109 g (1 mol) of 4-aminophenol and 101 g of triethylamine were dissolved in 700 ml of tetrahydrofuran. For this, 120.5 g (1 mol) of pivalic acid chloride were added dropwise at 10-15 ° C. with stirring. The mixture was stirred at room temperature for 2 hours and then poured into 3 liters of water. The deposited crystals were suction filtered and air dried. 165 g (85.5% of theory) 4-pivaloylamino-phenol.

Melting point: 168-170 ° C.

The substances of the formula (V) listed in the following examples were also prepared by the method given in Example 83.

Example 84

Schmelzpunkt: 122 - 124°C (nach Umkristallisation aus Tetrachlorkohlenstoff)

Melting point: 122 - 124 ° C (after recrystallization from carbon tetrachloride)

Example 85

Schmelzpunkt: 182 - 184°C (nach Umkristallisation aus Toluol)

Melting point: 182 - 184 ° C (after recrystallization from toluene)

Example 86

Melting point: 150 - 152 ° C (after recrystallization from toluene)

Example 87

Schmelzpunkt: 127 - 128°C

Melting point: 127 - 128 ° C

Usage example

In the following example of use, the following compound was used as the reference substance:

2-phenoxy-4,6-dimethyl-pyrimidine (known from US Pat. No. 3,126,271)

Example A

• Lösungsmittel: 5 Gewichtsteile Aceton
• Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether

Post emergence test

• Solvent: 5 parts by weight of acetone
• Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with the active substance preparation in such a way that the desired amounts of active substance are applied per unit area. The concentration of the spray liquor is chosen so that the desired amounts of active compound are applied in 2000 l of water / ha. After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

• 0 % = keine Wirkung (wie unbehandelte Kontrolle)
• 100 % = totale Vernichtung

It means:

• 0% = no effect (like untreated control)
• 100% = total annihilation

In this test, the compound according to Example 45 in the selective control of galinsoga, galium, sinapis, stellaria, echinochloa, panicum and poa in wheat and corn shows a substantially better herbicidal activity than the comparison substance (A).

Example B

• Testinsekt: Myzus persicae
• Lösungsmittel: 3 Gewichtsteile Aceton
• Emulgator: 1 Gewichtsteil Alkylarylpolyglykolether

Limit concentration test / root systemic effect

• Test insect: Myzus persicae
• Solvent: 3 parts by weight of acetone
• Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsifier is added and the concentrate is diluted with water to the desired concentration.

The active ingredient preparation is intimately mixed with soil. The concentration of the active ingredient in the preparation is practically irrelevant, the only decisive factor is the active ingredient preparation per unit volume of soil, which is given in ppm (= mg / 1). The treated soil is filled into pots and planted with cabbage (Brassica oleracea). The active ingredient can be taken up from the soil by the plant roots and transported to the leaves.

To prove the root systemic effect, only the leaves are populated with the test animals mentioned above after 7 days. After another 2 days, the evaluation is carried out by counting or estimating the dead animals. The root systemic effect of the active ingredient is derived from the number of killings. It is 100% when all test animals have been killed and 0% when as many test insects are still alive as in the untreated control.

In this test, the compounds according to Examples (14), (20) and (38) are notable for very good activity.

Claims (7)

1) Substituted carboxylic acid anilides of the formula

in which X represents oxygen or sulfur, R ^{1 represents} hydrogen, halogen, alkyl having 1 to 6 carbon atoms, trifluoromethyl, optionally substituted phenyl, alkoxy having 1 to 6 carbon atoms or alkyl mercapto having 1 to 6 carbon atoms, _R ^{2 represents} halogen or methyl, n represents 0, 1 or 2, _R ^{3 represents} hydrogen, halogen, optionally substituted alkyl having 1 to 6 carbon atoms, optionally substituted aryl, optionally substituted aralkyl or for the radicals -OR ⁶ or -SO _m - R ⁶ , where _R ^{6 represents} optionally substituted alkyl having 1 to 6 carbon atoms or optionally substituted aryl and m represents 0, 1 or 2,
and _R ⁴ and _R ⁵ independently of one another represent halogen or optionally substituted alkyl having 1 to 6 carbon atoms or _R ⁴ and _R ⁵ together with the adjacent carbon atom represent an optionally substituted, saturated or unsaturated carbocyclic ring having 3 to 8 ring carbon atoms. Substituted carboxylic acid anilides of the formula (I) in which X represents oxygen or sulfur, _R ^{1 represents} hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, trifluoromethyl, phenyl optionally substituted by chlorine, trifluoromethyl and / or methyl, alkoxy having 1 to 4 carbon atoms or alkyl mercapto having 1 to 4 carbon atoms, _R ^{2 represents} chlorine, bromine or methyl, n represents 0 or 1, _R ³ for hydrogen, fluorine, chlorine, bromine optionally substituted by fluorine, chlorine and / or bromine alkyl having 1 to 4 carbon atoms, optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, methoxy and / or methyl, phenyl optionally substituted by fluorine, chlorine, bromine, trifluoromethyl, methoxy and / or methyl substituted benzyl or the radicals -OR ⁶ or -SO _m R ⁶ , wherein _R ^{6 represents} alkyl with 1 to 4 carbon atoms optionally substituted by fluorine, chlorine and / or bromine or phenyl optionally substituted by fluorine, chlorine, bromine and / or alkyl with 1 to 4 carbon atoms and m represents 0, 1 or 2,
and _R ⁴ and _R ⁵ independently of one another for fluorine, chlorine, Are bromine or optionally substituted by fluorine, chlorine and / or bromine alkyl having 1 to 4 carbon atoms or _R ⁴ and R ⁵ together with the adjacent carbon atom represent a saturated or unsaturated carbocyclic ring having 3 to 7 ring carbon atoms which is optionally substituted by fluorine, chlorine and / or alkyl having 1 to 4 carbon atoms. 3) Process for the preparation of substituted carboxylic acid anilides of the formula

in which X represents oxygen or sulfur, _R ^{1 represents} hydrogen, halogen, alkyl having 1 to 6 carbon atoms, trifluoromethyl, optionally substituted phenyl, alkoxy having 1 to 6 carbon atoms or alkyl mercapto having 1 to 6 carbon atoms, _R ^{2 represents} halogen or methyl, n represents 0, 1 or 2, _R ^{3 represents} hydrogen, halogen, optionally substituted alkyl having 1 to 6 carbon atoms, optionally substituted aryl, optionally substituted aralkyl or the radicals -OR ⁶ or -SO _m -R ⁶ , where _R ^{6 represents} optionally substituted alkyl having 1 to 6 carbon atoms or optionally substituted aryl and m represents 0, 1 or 2,
and _R ⁴ and _R ⁵ independently of one another represent halogen or optionally substituted alkyl having 1 to 6 carbon atoms or _R ⁴ and R ⁵ together with the adjacent carbon atom represent an optionally substituted, saturated or unsaturated carbocyclic ring having 3 to 8 ring carbon atoms,
characterized in that one a) Aniline derivatives of the formula

in which R ¹ , R ² , X and n have the meaning given above,
either ) with acid halides of the formula

in which _R ³ , _R ⁴ and _R ^{5 have} the meaning given above and Y represents halogen,
if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder,
or ß) with symmetrical carboxylic anhydrides of the formula

in which _R ³ , _R ⁴ and R ^{5 have} the meaning given above,
if appropriate in the presence of a diluent, with asymmetric acid anhydrides of the formula

in which _R ³ , _R ⁴ and _R ^{5 have} the meaning given above and R represents alkyl having 1 to 4 carbon atoms or phenyl,
if appropriate in the presence of a diluent.
or δ) with compounds of the formula

in more _R ³ , _R ⁴ and _R ^{5 have} the meaning given above,
if appropriate in the presence of a diluent, b) pyrimidine derivatives of the formula

in which R ^{1 has} the meaning given above and Hal stands for halogen, with acylaniline derivatives of the formula

in which _R ² , _R ³ , R ⁴ , _R ⁵ , _X and n have the meaning given above,
in the presence of an acid binder and optionally in the presence of a diluent. 4) Herbicidal agents, characterized by a content of at least one substituted carboxylic acid anilide of the formula (I) according to Claims 1 and 3. 5) Weed control method, thereby characterized in that substituted carboxylic acid anilides of the formula (I) according to Claims 1 and 3 are applied to the weeds and / or their habitat. 6) Use of substituted carboxanilides of the formula (I) according to Claims 1 and 3 for combating weeds. 7) Process for the preparation of herbicidal compositions, characterized in that substituted carboxylic anilides of the formula (I) according to Claims 1 and 3 are mixed with extenders and / or surface-active substances.